Oral compositions containing gel networks

ABSTRACT

The present invention is directed to an oral composition containing a gel network phase comprising: (i) one or more fatty amphiphiles, (ii) one or more surfactants, and (iii) one or more solvents; and an oral carrier phase. In certain embodiments, the gel network is used to structure the oral composition. The present invention is also directed to a method of forming an oral composition containing a gel network.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application No.60/848,335, filed Sep. 29, 2006.

FIELD OF THE INVENTION

The present invention relates to an oral composition containing a gelnetwork.

BACKGROUND OF THE INVENTION

The rheology of oral care composition, particularly dentifrices, is verychallenging to formulate. The composition must not be too thick so itcan easily dispense out of a tube but thick enough to stand up on atoothbrush without sinking into the bristles. The viscosity of the oralcomposition must remain stable over time as not to continue to thickenso the oral composition remains easy to dispense during the shelf life.Once dispensed from a container, the oral composition should not bestringy or sticky as to be messy for a consumer to use. The oralcomposition must also easily disperse once in the mouth and create afoam. It is also desired that the oral composition not stick to a sinkor leave difficult to remove hard dried residue. In addition tobalancing the viscosity and shear thinning to formulate acceptablerheology, the oral composition must also be stable and keep activesingredients, such as fluoride, available.

In addition to the above requirement for a consumer desired oralcomposition, it is also desired that oral composition be relatively easyto process. The oral composition must have the desired rheology andshelf stability as described above but also be viscous enough to quicklyfill the oral composition into a container. It is also desired that theprocess not require special equipment and that the time to process notbe long. Typically, oral compositions are thickened with a polymericthickener. Polymeric thickeners may require a hydration step which canlimit processing flexibility and cause aeration problems. It is alsodesired that the thickening system of an oral composition be low costand comprise commonly available ingredients.

Based on the foregoing, there is a need for continuously improvedthickening or structuring systems for oral compositions. None of theexisting art provides all of the advantages and benefits of the presentinvention.

SUMMARY OF THE INVENTION

The present invention is directed to an oral composition containing agel network phase comprising: (i) one or more fatty amphiphiles, (ii)one or more secondary surfactants, and (iii) one or more solvents; andan oral carrier phase. The gel network phase can be used to structurethe oral composition. In some embodiments, the oral composition is adentifrice or a concentrated dentifrice. The fatty amphiphile can be asingle fatty alcohol or a combination of fatty alcohols, such as cetylalcohol and stearyl alcohol. Optionally, a surfactant, such as sodiumlauryl sulfate, can be added to the oral carrier phase in addition tothe secondary surfactant being in the gel network phase. The gel networkphase may provide the desired rheology without the use of a thickeningagent but optionally, a thickening agent may still be used. Thethickening agents may be used in a thickening amount or the oralcomposition may be essentially free of thickening agents. The oralcomposition may contain more than one gel network, such as a gel networkfor delivery or sequestration of non-compatible materials. The presentinvention is further directed to a method of using an effective amountof the oral composition in the oral cavity.

The present invention also is directed to a process of making the oralcomposition described above. In one method of making the oralcomposition, a fatty amphiphile, secondary surfactant, and solvent arecombined at a temperature sufficient to allow partitioning of thesecondary surfactant and solvent into the fatty amphiphile. This mixtureis then cooled below the chain melt temperature of the fatty amphiphileto form a gel network. Once the gel network is formed, oral carriermaterials are added to the gel network to form the oral composition.Optionally, some oral carrier materials may be added with the materialsfor the gel network or may be added when the gel network materials arecooling. An additional surfactant may be post-added, meaning added afterthe gel network is formed.

These and other features, aspects, and advantages of the presentinvention will become evident to those skilled in the art from a readingof the present disclosure.

DETAILED DESCRIPTION OF THE INVENTION

While the specification concludes with claims which particularly pointout and distinctly claim the invention, it is believed the presentinvention will be better understood from the following description.

All percentages, parts and ratios are based upon the total weight of thecompositions of the present invention, unless otherwise specified. Allsuch weights as they pertain to listed ingredients are based on theactive level and, therefore, do not include solvents or by-products thatmay be included in commercially available materials, unless otherwisespecified. The term “weight percent” may be denoted as “wt. %” herein.

All molecular weights as used herein are weight average molecularweights expressed as grams/mole, unless otherwise specified.

Herein, “comprising” means that other steps and other ingredients whichdo not affect the end result can be added. This term encompasses theterms “consisting of” and “consisting essentially of”. The compositionsand methods/processes of the present invention can comprise, consist of,and consist essentially of the essential elements and limitations of theinvention described herein, as well as any of the additional or optionalingredients, components, steps, or limitations described herein.

Herein, “effective amount” means an amount of a compound or compositionsufficient to significantly induce a positive benefit, preferably anoral health benefit, but low enough to avoid serious side effects, i.e.,to provide a reasonable benefit to risk ratio, within the sound judgmentof a skilled artisan.

By “oral composition” is meant a product, which in the ordinary courseof usage, is not intentionally swallowed for purposes of systemicadministration of particular therapeutic agents, but is rather retainedin the oral cavity for a time sufficient to contact substantially all ofthe dental surfaces and/or oral tissues for purposes of oral activity.The oral composition of the present invention may be in various formsincluding toothpaste, dentifrice, tooth gel, liquid gel, subgingivalgel, foam, mouse, or denture product. The oral composition may also be arinse thickened by a gel network. The oral composition may also beincorporated onto strips or films for direct application or attachmentto oral surfaces.

The term “dentifrice”, as used herein, means paste, gel, powder, orliquid formulations unless otherwise specified, used to clean thesurfaces of the oral cavity. The dentifrice composition may be a singlephase composition or may be a combination of two or more separatedentifrice compositions. The dentifrice composition may be in anydesired form, such as deep striped, surface striped, multilayered,having the gel surrounding the paste, or any combination thereof. Eachdentifrice composition in a dentifrice comprising two or more separatedentifrice compositions may be contained in a physically separatedcompartment of a dispenser and dispensed side-by-side.

The term “dispenser”, as used herein, means any pump, tube, package, orcontainer suitable for dispensing oral compositions.

The term “teeth”, as used herein, refers to natural teeth as well asartificial teeth or dental prosthesis.

The term “polymer” as used herein shall include materials whether madeby polymerization of one type of monomer or made by two (i.e.,copolymers) or more types of monomers.

The term “water soluble” as used herein means that the material issoluble in water in the present composition. In general, the materialshould be soluble at 25° C. at a concentration of 0.1% by weight of thewater solvent, preferably at 1%, more preferably at 5%, more preferablyat 15%.

The term “secondary surfactant” as used herein means a surfactant otherthan a fatty amphiphile. Various types of suitable surfactants arelisted below. There may be more than one secondary surfactant. Therewill be at least one secondary surfactant in the gel network phase.There may be another surfactant in the oral carrier phase.

The oral compositions of the present invention comprise a dispersed gelnetwork phase and an oral carrier phase. To the naked eye, the dispersedgel network phase and the oral carrier phase cannot be distinguished.The phases are immiscible within each other. However, components of eachphase, particularly water soluble components, may migrate to the otherphase. For example, a secondary surfactant is required in the gelnetwork phase but a portion of the secondary surfactant may migrate tothe oral carrier phase. Similarly, a flavor added to the oral carrierphase may migrate to the gel network phase. Each of the essentialcomponents, as well as preferred or optional components, is described indetail hereinafter.

A. Gel Network

The oral compositions of the present invention comprise a dispersed gelnetwork phase comprising a fatty amphiphile. As used herein, the term“gel network” refers to a lamellar or vesicular solid crystalline phasewhich comprises at least one fatty amphiphile as specified below, atleast one secondary surfactant as specified below, and a solvent asspecified below. The lamellar or vesicular phase comprises bi-layersmade up of a first layer comprising the fatty amphiphile and thesecondary surfactant and alternating with a second layer comprising thesolvent. For the lamellar crystalline phase to form, the fattyamphiphile and secondary surfactant must be dispersed within thesolvent. The term “solid crystalline”, as used herein, refers to thestructure of the lamellar or vesicular phase which forms at atemperature below the chain melt temperature of the layer in the gelnetwork comprising the one or more fatty amphiphiles. The chain melttemperature may be measured by differential scanning calorimetry, amethod of which is described in the Examples below.

The gel network in the oral composition is used to structure the oralcomposition. The structuring provided by the gel network provides thedesired rheology or viscosity by thickening the oral composition. Thestructuring can be done without the need for polymeric thickeningagents, however, polymeric thickeners or other agents could be used inaddition to the gel network to structure the oral composition.

Gel networks, generally, are further described by G. M. Eccleston,“Functions of Mixed Emulsifiers and Emulsifying Waxes in DermatologicalLotions and Creams”, Colloids and Surfaces A: Physiochem. and Eng.Aspects 123-124 (1997) 169-182; and by G. M Eccleston, “TheMicrostructure of Semisolid Creams”, Pharmacy International, Vol. 7,63-70 (1986).

According to this embodiment of the present invention, the gel networkcomponent of the present invention may be prepared by heating the fattyamphiphile, the secondary surfactant, and solvent to a level in therange of about 50° C. to about 90° C. and mixing. This mixture is cooledto a level in the range of about 20° C. to about 35° C. by, for example,passing the mixture through a heat exchanger. As a result of thiscooling step, the fatty amphiphile and the secondary surfactantcrystallize to form a solid crystalline gel network. The oral carrierscan be added at any time during this process.

Alternative methods of preparing the gel network component includesonication and/or milling of the fatty amphiphile, the secondarysurfactant, and solvent, while these components are heated, to reducethe particle size of the melted fatty amphiphile phase. This results inan increase in surface area of the fatty amphiphile phase, which allowsthe secondary surfactant and the solvent to swell the fatty amphiphilephase. Another suitable variation in preparing the gel network includesheating and mixing the fatty amphiphile and the secondary surfactantfirst, and then adding that mixture to the solvent.

An equilibrated lamellar dispersion (“ELD”) is formed in the final oralcomposition. The ELD is a dispersed lamellar or vesicular phaseresulting from the gel network component substantially equilibratingwith oral carriers and other optional components.

The presence of the gel network in the oral composition in the form ofthe ELD can be confirmed by means known to one of skill in the art, suchas X-ray analysis, optical microscopy, electron microscopy, anddifferential scanning calorimetry. Methods of X-ray analysis anddifferential scanning calorimetry are described in the Examples below.

In an embodiment of the present invention, the weight ratio of the fattyamphiphile to the surfactant in the gel network component is greaterthan about 1:5, preferably from about 1:3 to about 100:1, morepreferably greater than about 1:1 to about 20:1, and even morepreferably greater than about 2:1 to about 10:1.

1. Fatty Amphiphile

The gel network component of the present invention comprises at leastone fatty amphiphile. As used herein, “fatty amphiphile” refers to acompound having a hydrophobic tail group of R₁ as defined below and ahydrophilic head group which does not make the compound water soluble(immiscible), wherein the compound also has a net neutral charge at thepH of the oral composition. The term “water soluble”, as used herein,means that the material is soluble in water in the present composition.In general, the material should be soluble at 25° C. at a concentrationof 0.1% by weight of the water solvent, preferably at 1%, morepreferably at 5%, more preferably at 15%.

The fatty amphiphile of the present invention may be characterized as acompound having a Hydrophilic-Lipophilic Balance (“HLB”) of 6 or less.The HLB, as used herein, is the standard HLB according to Griffin, J.Soc. Cosm. Chem., vol. 5, 249 (1954).

The oral compositions of the present invention comprise fatty amphiphilein an amount from about 0.05% to about 30%, preferably from about 0.1%to about 20%, and more preferably from about 0.5% to about 10%, byweight of the oral composition. The amount of fatty amphiphile will bechosen based on the formation of the gel network and the composition ofthe oral formulation. For example, an oral composition containing lowamounts of water may require about 1% of a fatty amphiphile whereas anoral composition with higher amounts of water may require 6% or more ofa fatty amphiphile.

According to the present invention, suitable fatty amphiphiles, orsuitable mixtures of two or more fatty amphiphiles, preferably have amelting point of at least about 45° C. In some embodiments, it ispreferred that the melting point be at least about 50° C. or greaterthan about 55° C. or greater than about 60° C. The melting point, asused herein, may be measured by a standard melting point method asdescribed in U.S. Pharmacopeia, USP-NF General Chapter <741>“Meltingrange or temperature”. The melting point of a mixture of two or morematerials is determined by mixing the two or more materials at atemperature above the respective melt points and then allowing themixture to cool. If the resulting composite is a homogeneous solid belowabout 45° C., then the mixture has a suitable melting point for use inthe present invention. A mixture of two or more fatty amphiphiles,wherein the mixture comprises at least one fatty amphiphile having anindividual melting point of less than about 45° C., still is suitablefor use in the present invention provided that the composite meltingpoint of the mixture is at least about 45° C.

According to the present invention, suitable fatty amphiphiles have ahydrophobic tail group of R₁. As used herein, R₁ is an alkyl, alkenyl(containing up to 3 double bonds), alkyl aromatic, or branched alkylgroup of C₁₂-C₇₀ length. Non-limiting examples of alkyl, alkenyl, orbranched alkyl groups suitable for the fatty amphiphiles of the presentinvention include lauryl, tridecyl, myristyl, pentadecyl, cetyl,heptadecyl, stearyl, arachidyl, behenyl, undecylenyl, palmitoleyl,oleyl, palmoleyl, linoleyl, linolenyl, arahchidonyl, elaidyl,elaeostearyl, erucyl, isolauryl, isotridecyl, isomyristal,isopentadecyl, petroselinyl, isocetyl, isoheptadecyl, isostearyl,isoarachidyl, isobehnyl, gadoleyl, brassidyl, and technical-grademixture thereof.

As used herein, R₁ also may be a branched alkyl group prepared byalkaline condensation of alcohols to give higher molecular weight,branched isoalcohols. These branched isoalcohols are referred to in theart as Guerbet alcohols.

R₁ may be alkyl, alkenyl or branched carbon chains of vegetable origin,such as wheat germ, sunflower, grape seed, sesame, maize, apricot,castor, avocado, olive, soybean, sweet almond, palm, rapeseed, cottonseed, hazelnut, macadamia, karite, jojoba, alfalfa, poppy, pumpkinseed,sesame, cucumber, blackcurrant, evening primrose, millet, barley,quinoa, rye, safflower, candlenut, passion flower or musk rose oil, andkarite butter.

Suitable fatty amphiphiles of the present invention also have ahydrophilic head group which does not make the compound water soluble,such as in compounds having an HLB of 6 or less. Non-limiting examplesof classes of compounds having such a hydrophilic head group includefatty alcohols, alkoxylated fatty alcohols, fatty phenols, alkoxylatedfatty phenols, fatty amides, alkyoxylated fatty amides, fatty amines,fatty alkylamidoalkylamines, fatty alkyoxyalted amines, fattycarbamates, fatty amine oxides, fatty acids, alkoxylated fatty acids,fatty diesters, fatty sorbitan esters, fatty sugar esters, methylglucoside esters, fatty glycol esters, mono, di & tri glycerides,polyglycerine fatty esters, alkyl glyceryl ethers, propylene glycolfatty acid esters, cholesterol, ceramides, fatty silicone waxes, fattyglucose amindes, and phospholipids.

To form the gel network component of the present invention, individualfatty amphiphile compounds or combinations of two or more differentfatty amphiphile compounds may be selected. The following providesnon-limiting examples of classes of compounds from which one or morefatty amphiphiles suitable for use in the present invention may beselected.

a. Fatty Alcohols/Alkoxylated Fatty Alcohol Ethers

Fatty amphiphiles of the present invention may be selected from fattyalcohol compounds or alkoxylated fatty alcohol ether compounds accordingto the following formula:R₁—(OR₂)_(k)—OHwherein R₁ is as described above; R₂ is a C₁-C₅ carbon chain which maybe branched or hydroxy substituted; and k is a number ranging from about0 to about 5.

The fatty alcohols useful herein are those having from about 12 to about60 carbon atoms, preferably from about 16 to about 60 carbon atoms.These fatty alcohols may be straight or branched chain alcohols and maybe saturated or unsaturated. Non-limiting examples of suitable fattyalcohols include cetyl alcohol, stearyl alcohol, arachidyl alcohol,behenyl alcohol, eicosyl alcohol, C20-40 alcohols, C30-50 alcohols,C40-60 alcohols, and mixtures thereof.

Suitable alkoxylated fatty alcohol ethers include addition products of 1to 5 mol of ethylene oxide with a linear fatty alcohol having about 12to about 60 carbon atoms, which are all adducts obtainable by the knownindustrial oxyethylation processes. Also suitable are the polyethyleneoxide condensates of alkyl phenols, for example, the condensationproducts of alkyl phenols having an alkyl group containing from about 12to about 60 carbon atoms in either a straight chain or branched chainconfiguration, with ethylene oxide, wherein the ethylene oxide ispresent in amounts equal to from about 1 to about 5 moles of ethyleneoxide per mole of alkyl phenol. Further suitable alkoxylated fattyalcohol ethers include those derived from the condensation of ethyleneoxide with the product resulting from the reaction of propylene oxideand ethylene diamine products.

Non-limiting examples of suitable alkoxylated fatty alcohol ethersinclude steareth-2, beheneth-2, beheneth-5, beheneth-10, C20-40Pareth-3, C20-40 Pareth-10, C30-50 Pareth-3, and C30-50-Pareth- 10.

In one embodiment, a combination of fatty alcohols such as cetyl andstearyl alcohol is preferred. The ratio of cetyl to stearyl alcohol canbe from about 4:1 to about 1:4, preferably from about 2:1 to about 1:2,and in some embodiments 1:1.

b. Di-Fatty Ethers

Fatty amphiphiles of the present invention may be selected from di-fattyether compounds according to the following formula:R′₁—(OR₂)_(k)—Z—(R₂O)_(l)—R″₁wherein R₁ is as described above; R₂ is a C₁-C₅ carbon chain which canbe branched or hydroxy substituted; k and I each is independently anumber such that the sum (k+l) has a value ranging from 1 to 30; and Zis an ether (i.e., —O—) or an amine (i.e., —NR₂—, wherein R₂ is asdescribed immediately above).

Compounds of the above formula in which Z is an ether (i.e., dialkyloxyethyl ethers) may be prepared by esterification processes, which areknown in the art, of fatty alcohols and fatty alkyl oxyethanols.Compounds of the above formula in which Z is an amine group may beobtained, for example, from triethanolamine by O-alkylation with 2 molof a sulfuric half-ester salt of a C₁₂-C₆₀ fatty alcohol, according to aprocess for the preparation of ether amines described in DE 35 04 242.

Non-limiting examples of suitable di-fatty ether compounds includedicetylstearyl ether, dicetylstearyl dioxyethyl ether, andN,N-bis(2-cetylstearyl-oxyethyl)arminoethanol.

c. Fatty Amides/Fatty Alkanolamides/Fatty Alkoxylated Amides

Fatty amphiphiles of the present invention also may be selected fromfatty amide compounds according to the following formula:

wherein R₁ is as described above; R₂ and R₃ each is independently aC₁-C₅ carbon chain which can be branched or hydroxy substituted; k and leach is independently a number such that the sum (k+l) has a valueranging from 0 to 10; and X and Y are each independently selected fromhydrogen, a C₁-C₄ carbon chain which can be branched or hydroxysubstituted, morpholine, or a C₅-C₅₀ carbon chain bonded via an amide,ester, or ether linkage.

Non-limiting examples of suitable fatty amides, fatty alkanolamides orfatty alkoxylated amides include Cocamide, Cocamide Methyl MEA, CocoylGlutamic Acid, Erucamide, Lauramide, Oleamide, Palmitamide, Stearamide,Stearyl Erucamide, Behenamide DEA, Behenamide MEA, Cocamide DEA,Cocamide MEA, Cocamide MIPA, Hydroxyethyl Stearamide-MIPA, HydroxypropylBisisostearamide MEA, Hydroxypropyl Bislauramide MEA, HydroxystearamideMEA, Isostearamide DEA, Isostearamide MEA, Isostearamide MIPA, LauramideDEA, Lauramide MEA, Lauramide MIPA, Myristamide DEA, Myristamide MEA,Myristamide MIPA, Palmamide DEA, Palmamide MEA, Palmamide MIPA,Palmitamide DEA, Palmitamide MEA, PEG-20 Cocamide MEA, Stearamide AMP,Stearamide DEA, Stearamide DEA-Distearate, Stearamide DIBA-Stearate,Stearamide MEA, Stearamide MEA-Stearate, Stearamide MIPA, PEG-2Cocamide, PEG-3 Cocamide, PEG-4 Cocamide, PEG-5 Cocamide, PEG-6Cocamide, PEG-7 Cocamide, PEG-3 Lauramide, PEG-5 Lauramide, PEG-3Oleamide, PEG-9 Oleamide, PEG-4 Stearamide, PEG-10 Stearamide, PPG-2Cocamide, PPG-2 Hydroxyethyl Cocamide, PPG-2 HydroxyethylCoco/Isostearamide, Ceramide 1, Ceramide 2, Ceramide 3, Ceramide 4, andCeramide 5.

d. Fatty Carbamates

Fatty amphiphiles of the present invention may be selected from fattycarbamate compounds according to the following formula:

wherein R₁ is as described above; R₂ and R₃ each is independently aC₁-C₅ carbon chain which can be branched or hydroxy substituted; k and leach is independently a number such that the sum (k+l) has a valueranging from 0 to 10; and X and Y each is independently selected fromhydrogen, a C₁-C₄ carbon chain which can be branched or hydroxysubstituted, morpholine, or a C₅-C₅₀ carbon chain bonded via an amide,ester, or ether linkage.

Non-limiting examples of suitable fatty carbamates include cetylcarbamate, stearyl carbamate, PEG-2 stearyl carbamate, PEG-4 stearylcarbmate, and behenyl caibamate.

e. Fatty Alkylamido Alkylamines

Fatty amphiphiles of the present invention also may be selected fromfatty alkylamido alkylamine compounds according to the followingformula:

wherein R₁ is as described above; R₂ and R₃ each is independently aC₁-C₅ carbon chain which can be branched or hydroxy substituted; k and leach is independently a number such that the sum (k+l) has a valueranging from 0 to 10; X and Y each is independently selected fromhydrogen, a C₁-C₄ carbon chain which can be branched or hydroxysubstituted, morpholine, or a C₅-C₅₀ carbon chain bonded via an amide,ester, or ether linkage; and n is a number ranging from about 1 to about4.

Non-limiting examples of suitable fatty alkylamido alkylamine compoundsinclude stearamidoethyl diethanolamine, stearamidopropyl morpholine,stearamidopropyl dimethylaamine stearate, stearamidopropyldimethylamine, stearamidoethyl diethylamine, stearamidoethyldiethanolamine, isostearamidomorpholine stearatebehenamidopropyldimethylamine, behenamidopropyldiethylamine,behenamidoethyldiethyl-amine, cocamidopropyl dimethylaminebehenamidoethyldimethylamine, arachidamidopropyldimethylamine,arachidamido-propyidiethylamine, arachidamidoethyidiethylamine,arachidamidoethyidimethylamine, and mixtures thereof.

f. Fatty Amines/Fatty Alkanolamines/Fatty Alkoxylated Amines

Fatty amphiphiles of the present invention further may be selected fromfatty amine compounds according to the following formula:

wherein R₁ is as described above; and R′₅ and R″₅ are independentlyhydrogen or a C₁-C₅ carbon chain which can be branched or hydroxysubstituted.

Additionally, fatty amphiphiles of the present invention may be selectedfrom fatty alkoxylated amine compounds according to either one of thefollowing formulas:

wherein R₁ is as described above; R₂ and R₃ each is independently aC₁-C₅ carbon chain which can be branched or hydroxy substituted; k and leach is independently a number such that the sum (k+l) has a valueranging from 0 to 10; X and Y each is independently hydrogen, a C₁-C₄carbon chain which can be branched or hydroxy substituted, morpholine,or a C₅-C₅₀ carbon chain bonded via amide, ester, or ether linkage; n isa number ranging from about 1 to about 4; and Z is an ether (i.e., —O—)or an amine (i.e., —NH—).

Primary, secondary, and tertiary fatty amines are useful. Suitable fattyalkoxylated amine compounds include addition products of ethylene oxidewith a linear fatty alkylamine having 12 to 60 carbon atoms, all ofwhich are adducts obtainable by known industrial processes and which arecommercially available.

Non-limiting examples of suitable fatty amine and fatty alkoxylatedamine compounds include diethyllauramine, dicocamine, dimethylcocamineamine cetamine, stearamine, oleamine, behenamine, dimethylbehenamineamine, diethylbehenamine, dibehenylamine N-lauryl diethanolamine.TEA-diricinoleate, TEA-lauryl ether, diethylaminoethyl PEG-5 cocoate,diethylaminoethyl PEG-5 laurate, hydroxyethyl isostearyloxyisopropanolamine, PEG-2 cocamine, PEG-5 cocamine, PEG-10 cocamine, PEG-5isodecyloxypropylamine, PEG-2 lauramine, PEG-2 oleamine, PEG-5 oleamine,PEG-10 oleamine, PEG-2 stearamine, PEG-5 stearamine, PEG-10 stearamine,PPG-2 cocamine, PPG-2 hydrogenated tallowamine, PPG-2 tallowamine, andPPG-3 tallow aminopropylamine.

g. Fatty Amine Oxides

Fatty amphiphiles of the present invention also may be selected fromfatty amine oxide compounds according to the following formula:

wherein R₁ is as described above; R₂ and R₃ each is independently aC₁-C₅ carbon chain which can be branched or hydroxy substituted; k and leach is independently a number such that the sum (k+l) has a valueranging from 0 to 10; X and Y each is independently hydrogen, a C₁-C₄carbon chain which can be branched or hydroxy substituted, morpholine,or a C₅-C₅₀ carbon chain bonded via an amide, ester, or ether linkage; Zis an ether (i.e., —O—) or an amide (i.e., —C(O)—NH—) linkage; and n isa number ranging from about 1 to about 4. In accord with knownconvention, the arrow in the above formula is representative of asemi-polar bond.

Non-limiting examples of suitable amine oxide compounds includedimethyl-dodecylamine oxide, oleyldi(2-hydroxyethyl) amine oxide,dimethyltetradecylamine oxide, di(2-hydroxyethyl)-tetradecylamine oxide,dimethylhexadecylamine oxide, behenamine oxide, cocamine oxide,decyltetradecylamine oxide, dihydroxyethyl C12-15 alkoxypropylamineoxide, dihydroxyethyl cocamine oxide, dihydroxyethyl lauramine oxide,dihydroxyethyl stearamine oxide, dihydroxyethyl tallowamine oxide,hydrogenated palm kernel amine oxide, hydrogenated tallowamine oxide,hydroxyethyl hydroxypropyl C12-15 alkoxypropylamine oxide, lauramineoxide, myristamine oxide, myristyl/cetyl amine oxide,oleamidopropylamine oxide, oleamine oxide, palmitamine oxide, PEG-3lauramine oxide, potassium trisphosphonomethylamine oxide, stearamineoxide, and tallowamine oxide.

h. Fatty Acid/Alkoxylated Fatty Acid

Fatty amphiphiles of the present invention also may be selected fromfatty acid or alkoxylated fatty acid compounds according to thefollowing formula:

wherein R₁ is as described above; R₂ is a C₁-C₅ carbon chain which canbe branched or hydroxy substituted; and k is a number ranging from about0 to about 5.

Non-limiting examples of suitable fatty acids and alkoxylated fattyacids include behenic acid, C10-40 hydroxyalkyl acid, C32-36 isoalkylacid coconut acid, erucic acid, hydroxystearic acid, lauric acid,linoleic acid, myristic acid, oleic acid, palmitic acid, PEG-8 behenate,PEG-5 cocoate, PEG-10 cocoate, PEG-2 laurate, PEG-4 laurate PEG-6laurate, PEG-8 laurate, PEG-9 laurate, PEG-10 laurate, PEG-7 oleate,PEG-2 stearate, PEG-3 stearate, PEG-4 stearate, PEG-5 stearate, PEG-6stearate, PEG-7 stearate, PEG-8 stearate, PEG-9 stearate, PEG-10stearate, polyglyceryl-2-PEG-4 stearate, PPG-2 isostearate, and PPG-9laurate.

i. Fatty Esters

Fatty amphiphiles of the present invention may be selected from fattyester compounds according to the following formula:

wherein R₁ is as described above; R₂ is a C₁-C₅ carbon chain which canbe branched or hydroxy substituted; k is a number ranging from about 1to about 5; and R₆ is a C₁-C₄₀ carbon chain or an alkylcarbonyl (i.e.,

wherein R₇ is a C₁-C₄₀ carbon chain).

These suitable fatty esters include esters with hydrocarbyl chainsderived from fatty acids or alcohols (e.g., mono-esters, polyhydricalcohol esters, and di- and tri-carboxylic acid esters). The hydrocarbylradicals of the fatty esters hereof may include or have covalentlybonded thereto other compatible functionalities, such as amides andalkoxy moieties (e.g., ethoxy or ether linkages, etc.).

Non-limiting examples of suitable fatty ester compounds includeisopropyl isostearate, hexyl laurate, isohexyl laurate, isohexylpalmitate, isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecylstearate, decyl stearate, isopropyl isostearate, dihexyldecyl adipate,lauryl lactate, myristyl lactate, cetyl lactate, oleyl stearate, oleyloleate, oleyl myristate, lauryl acetate, cetyl propionate, and oleyladipate.

Fatty amphiphiles of the present invention also may be selected fromother fatty ester compounds according to the following formula:

wherein R′₈, R″₈, and R′″₈ each is independently selected from hydrogen,hydroxy, or a C₁-C₄ carbon chain which can be branched or hydroxysubstituted; k′, k″, and k′″ each is independently a number such thatthe sum (k′+k″+k′″) has a value ranging from 0 to 15; R′₂, R″₂, and R′″₂each is.independently selected from a C₁-C₅ carbon chain which can bebranched or hydroxy substituted; and where R′₁₀, R″₁₀, R′″₁₀ each isindependently selected form hydrogen or R₁ , where R₁ is as definedabove, provided that at least one of R′₁₀, R″₁₀, and R′″₁₀ is a R1group.

Still other suitable fatty esters are di- and tri-alkyl and alkenylesters of carboxylic acids, such as esters of C₄ to C₈ dicarboxylicacids (e.g., C₁ to C₂₂ esters, preferably C₁ to C₆, of succinic acid,glutaric acid, and adipic acid). Specific non-limiting examples of di-and tri-alkyl and alkenyl esters of carboxylic acids include isocetylstearyol stearate, stearyl citrate, distearyl citrate and tristearylcitrate.

Fatty amphiphiles of the present invention further may be selected fromother fatty ester compounds according to the following formula:

wherein R′₂, R″₂, and R′″₂ each is independently selected from a C₁-C₅carbon chain which can be branched or hydroxy substituted; R′₈, R″₈, andR′″₈ each is independently selected from hydrogen, hydroxy, or C₁-C₄carbon chain which can be branched or hydroxy substituted; k′, k″, andk′″ each is independently a number such that the sum (k′+k″+k′″ ) has avalue ranging from 0 to 15; and R′₉, R″₉, and R′″₉ each is independentlyselected from hydrogen or alkylcarbonyl (i.e.,

wherein R₁ is as described above), provided that at least one of R′₉,R″₉, and R′″₉ is a

group.

Other suitable fatty esters are those known as polyhydric alcoholesters. Such polyhydric alcohol esters include alkylene glycol esters,such as ethylene glycol mono and di-fatty acid esters, diethylene glycolmono- and di-fatty acid esters, polyethylene glycol mono- and di-fattyacid esters, propylene glycol mono- and di-fatty acid esters,polypropylene glycol monooleate, polypropylene glycol 2000 monostearate,ethoxylated propylene glycol monostearate, glyceryl mono- and di-fattyacid esters, polyglycerol poly-fatty acid esters, ethoxylated glycerylmonostearate, 1,3-butylene glycol monostearate, 1,3-butylene glycoldistearate, polyoxyethylene polyol fatty acid ester.

Still other fatty esters suitable for use in the compositions of thepresent invention are glycerides, including, but not limited to, mono-,di-, and tri-glycerides, preferably mono- and di-glycerides, morepreferably mono-glycerides. For use in the compositions describedherein, the glycerides are preferably the mono-, di-, and tri-esters ofglycerol and long chain carboxylic acids, such as C₁₂ to C₂₂ carboxylicacids. A variety of these types of materials can be obtained fromvegetable and animal fats and oils, such as castor oil, safflower oil,cottonseed oil, corn oil, olive oil, cod liver oil, almond oil, avocadooil, palm oil, sesame oil, lanolin and soybean oil. Synthetic oilsinclude, but are not limited to, triolein and tristearin glyceryldilaurate.

j. Fatty Phosphorus Compounds

Fatty amphiphiles of the present invention may be selected from fattyphosphorus compounds according to the following formula:

wherein R₁ is as described above; R₂ is a C₁-C₅ carbon chain which canbe branched or hydroxy substituted; k is a number ranging from about 0to about 5; and R₅ is hydrogen or a C₁-C₄ carbon chain which can bebranched or hydroxy substituted. In accord with known convention, thearrow in the above formula is representative of a semi-polar bond.

Non-limiting examples of suitable fatty phosphorus compounds includedodecyldimethylphosphine oxide, tetradecyldimethylphosphine oxide,tetradecylmethylethylphosphine oxide,3,6,9,-trioxaoctadecyldimethylphosphine oxide, cetyldimethylphosphineoxide, 3-dodecoxy-2-hydroxypropyldi(2-hydroxyethyl) phosphine oxide,stearyldimethylphosphine oxide, cetylethylpropylphosphine oxide,oleyldiethylphosphine oxide, dodecyldiethylphosphine oxide,tetradecyldiethylphosphine oxide, dodecyldipropylphosphine oxide,dodecyldi(hydroxymethyl)phosphine oxide, dodecyldi(2-hydroxyethyl)phosphine oxide, tetradecylmethyl-2-hydroxypropylphosphine oxide,oleyldimethylphosphine oxide, and 2-hydroxydodecyldimethylphosphineoxide.

k. Fatty Sorbitan Derivatives

Fatty amphiphiles of the present invention also may be selected fromfatty sorbitan derivative compounds according to the following formula:

wherein R′₂, R″₂, R′″₂, and R″″₂ each is independently a C₁-C₅ carbonchain which can be branched or hydroxy substituted; R′₉, R″₉, R′″₉, andR″″₉ each is independently hydrogen or alkylcarbonyl (i.e.,

wherein R₁ is as described above), provided that at least one of R′₉,

R″₉, R′″₉, and R″″₉ is a group; and k′, k″, k′″, and k″″ each isindependently a number such that the sum (k′+k″+k′″+k″″) has a valueranging from 0 to 20.

Non-limiting examples of suitable fatty sorbitan derivatives includePEG-20 sorbitan cocoate, PEG-2 sorbitan isostearate, PEG-5 sorbitanisostearate, PEG-20 sorbitan isostearate, PEG-10 sorbitan laurate, PEG-3sorbitan oleate, PEG-6 sorbitan oleate, PEG-20 sorbitan oleate, PEG-3sorbitan stearate, PEG-4 sorbitan stearate, PEG-6 sorbitan stearate,PEG-4 sorbitan triisostearate, PEG-20 sorbitan triisostearate, PEG-2sorbitan trioleate, PEG-3 sorbitan tristearate, polyglyceryl-2 sorbitantetraethylhexanoate, sorbitan caprylate, sorbitan cocoate, sorbitandiisostearate, sorbitan dioleate, sorbitan distearate, sorbitanisostearate, sorbitan laurate, sorbitan oleate, sorbitan olivate,sorbitan palmitate, sorbitan sesquiisostearate, sorbitan sesquioleate,sorbitan sesquistearate, sorbitan stearate, sorbitan triisostearate,sorbitan trioleate, sorbitan tristearate, and sorbitan undecylenate.

1. Sucrose Polyesters

Fatty amphiphiles of the present invention may be selected from sucrosepolyester compounds according to the following formula:

wherein R′₉, R″₉, R′″₉, R″″₉, R′″″₉, R″″″₉, R′″″″₉, and R″″″″₉ each ishydrogen or alkylcarbonyl (i.e.,

wherein R₁ is as described above), provided that at least one of R′₉,R″₉, R′″₉, R″″₉, R′″″₉, R″″″₉, R′″″″₉, and R″″″″₉ is a

group.

Non-limiting examples of suitable sucrose polyester compounds includeSucrose Cocoate, Sucrose Dilaurate, Sucrose Distearate, SucroseHexaerucate, Sucrose Hexaoleate/Hexapalmitate/Hexastearate, SucroseHexapalmitate, Sucrose Laurate, Sucrose Mortierellate, SucroseMyristate, Sucrose Octaacetate, Sucrose Oleate, Sucrose Palmitate,Sucrose Pentaerucate, Sucrose Polybehenate, Sucrose Polycottonseedate,Sucrose Polylaurate, Sucrose Polylinoleate, Sucrose Polyoleate, SucrosePolypalmate, Sucrose Polysoyate, Sucrose Polystearate, SucroseRicinoleate, Sucrose Stearate, Sucrose Tetraisostearate, SucroseTetrastearate Triacetate, Sucrose Tribehenate, and Sucrose Tristearate.

m. Alkyl Sulfoxides

Fatty amphiphiles of the present invention further may be selected fromalkyl sulfoxide compounds according to the following formula:

wherein R₁ is as described above; R₂ is a C₁-C₅ carbon chain which canbe branched or hydroxy substituted; k is a number ranging from about 0to about 10; and X and Y each is independently selected from hydrogen ora C₁-C₄ carbon chain which can be branched or hydroxy substituted.

Non-limiting examples of suitable alkyl sulfoxide compounds includeoctadecyl methyl sulfoxide, 2-ketotridecyl methyl sulfoxide,3,6,9,-trioxaoctadecyl 2-hydroxyethyl sulfoxide, dodecyl methylsulfoxide, oleyl 3-hydroxypropyl sulfoxide, tetradecyl methyl sulfoxide,3-methoxytridecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide,and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

2. Surfactant

The gel network component of the present invention also comprises asecondary surfactant. As used herein, “surfactant” refers to one or moresurfactants which are combined with the fatty amphiphile and oralcarrier to form the gel network of the present invention. The secondarysurfactant is typically water soluble or miscible in the solvent or oralcarrier. The secondary surfactant may be characterized as a compoundhaving a Hydrophilic-Lipophilic Balance (“HLB”) of 6 or more andtypically from about 8 to about 30. The HLB, as used herein, is thestandard HLB according to Griffin, J. Soc. Cosm. Chem;, vol. 5, 249(1954). Preferably, the surfactant will be reasonably stable and foamthroughout a wide pH angle.

The oral compositions of the present invention comprise secondarysurfactant as part of gel network phase in an amount from about 0.01% toabout 15%, preferably from about 0.1% to about 10%, and more preferablyfrom about 0.3% to about 5%, by weight of the oral composition. In someembodiments, a diluted solution of surfactant in water is utilized. Inonce embodiment, the amount of surfactant is chosen based on the levelof foaming desired in the oral composition and on the irritation causedby the surfactant. Once the level of surfactant is chosen, then thelevel of fatty amphiphile that forms a gel network is chosen. Forexample, in oral compositions with low level of solvents, a greateramount of fatty amphiphile may be required whereas in oral compositionswith high level of solvents or water, a low level of fatty amphiphilemay be chosen.

Suitable secondary surfactants include anionic, zwitterionic,amphoteric, cationic, and nonionic surfactants. In one embodiment,anionic surfactants are preferred. The secondary surfactants may be acombination of more than one type of surfactants, such as an anionic andnonionic surfactant.

Anionic surfactants useful herein include the water-soluble salts ofalkyl sulfate having from 8 to 20 carbon atoms in the alkyl radical(e.g., sodium alkyl sulfate) and the water-soluble salts of sulfonatedmonoglycerides of fatty acids having from 8 to 20 carbon atoms.Preferred anionic surfactants for use as secondary surfactants of thepresent invention include sodium lauryl sulfate, sodium laurylsarcosinate, sodium cocoyl methyl taurate, sodium monoglyceride sulfate,sodium cetaryl sulfate, potassium cocoyl glycinate, socium laurylphosphate, sodium lauryl lactylate, sodium lauryl sulfoacetate, sodiumlauroyl glutamate, sodium lauryl isethionate, sodium laurethcarboxylate, sodium dodecyl benzenesulfonate, and combinations thereof.In one embodiment, sodium lauryl sulfate is a preferred secondarysurfactant. Many suitable anionic surfactants are disclosed by Agricolaet al., U.S. Pat. No. 3,959,458, issued May 25, 1976.

Nonionic surfactants useful herein can be broadly defined as compoundsproduced by the condensation of alkylene oxide groups (hydrophilic innature) with an organic hydrophobic compound which may be aliphatic oralkyl-aromatic in nature. Nonlimiting examples of suitable nonionicsurfactants include low molecular weight poloxamers (sold under thetrade name PLURONIC®), polyoxyethylene, polyoxyethylene sorbitan esters(sold under the trade name Tweens), polyoxyl 40 hydrogenated castor oil,fatty alcohol ethoxylates, polyethylene oxide condensates of alkylphenols, products derived from the condensation of ethylene oxide withthe reaction product of propylene oxide and ethylene diamine, ethyleneoxide condensates of aliphatic alcohols, long chain tertiary amineoxides, long chair tertiary phosphaine oxides, lauryl glucoside (soldunder the trade name PLANTERN 1200 UP®) and long chain dialkylsulfoxides. Suitable nonionic surfactants with a HLB of 7 or moreinclude sucrose laurate, sucrose cocoate, sucrose stearate; Steareth 20,21, or 100, and PEG 20 Sorbitan Monostearate (commercially available asTWEEN 60®).

Amphoteric surfactants suitable as a secondary surfactant in the presentinvention can be broadly described as derivatives of aliphatic secondaryand tertiary amines in which the aliphatic radical can be a straightchain or branched and wherein one of the aliphatic substituents containsfrom about 8 to about 18 carbon atoms and one contains an anionicwater-solubilzing group, such as carboxylate, sulfonate, sulfate,phosphate, or phosphonate. Other suitable amphoteric surfactants arebetains, such as cocamidopropyl betaine, lauryl dimethyl betaine (soldunder the trade name Macat LB), cetyl dimethyl betaine, andcocoamphodiacetate. Additional amphoteric surfactants and nonionicsurfactants can be found in Gieske et al., U.S. Pat. No. 4,051,234,issued Sep. 27, 1977. Examples of suitable cationic surfactants includecetyl pyridinium chloride, coamidopropyl PG dimonium chloride phosphate(Phospholipid CDM), myristylamidopropyl PG dimonium chloride phosphate(Phospholipid PTM), stearamidopropyl PG dimonium chloride phosphate(Phospholipid SV), steapyrium chloride (Catemol WPC), and other suitablecationic materials.

More than one surfactant of the above specified types may be used forthe secondary surfactant of the present invention.

Another secondary surfactant may also be added to the oral carrier phaseof the oral composition. This secondary surfactant is typically not partof the gel network as it does not participate in forming the gel networkstructure. The surfactant in the oral carrier phase may provide enhancedfoaming or a different foaming profile. The surfactant added to the oralcarrier phase may also aid in modifying viscosity and changing theflavor display. The addition of one or more surfactants to the oralcarrier phase can be called post-added surfactants. If the surfactant isadded above the phase transition temperature of the gel network, thesurfactant will typically be in the gel network phase. If the surfactantis added when the temperature of the composition is below the phasetransition temperature, the surfactant will typically be in the oralcarrier phase and be considered a post-added surfactant.

3. Solvents

The gel network component of the present invention also comprisessolvents, such as water or other suitable solvents. The solvent and thesecondary surfactant together contribute to the swelling of the fattyamphiphile. This, in turn, leads to the formation and the stability ofthe gel network. In addition to forming the gel network, the solvent canhelp to keep the dentifrice composition from hardening upon exposure toair and provide a moist feel in the mouth. The solvent, as used herein,refers to suitable solvents which can be used in the place of or incombination with water in the formation of the gel network of thepresent invention.

Suitable solvents for the present invention include water, ediblepolyhydric alcohols such as glycerin, diglycerin, triglycerin, sorbitol,xylitol, butylene glycol, erythritol, polyethylene glycol, propyleneglycol, and combinations thereof. Sorbitol, glycerin, water, andcombinations thereof are preferred solvents.

The oral compositions of the present invention comprise solvents as partof the gel network phase in an amount suitable to achieve a gel networkwhen combined with fatty amphiphile and secondary surfactant accordingto the present invention. In a preferred embodiment, the oralcompositions of the present invention comprise as part of the gelnetwork phase at least about 0.05% of a solvent, by weight of the oralcomposition. The solvent may be present in the oral composition inamount of from about 0.1% to about 99%, from about 0.5% to about 95%,and from about 1% to about 90%. The solvent is present in the gelnetwork phase and may also be added or present in the oral carrierphase.

B. Oral Carrier Phase

The oral compositions of the present invention comprises an oral carrierphase. The compositions comprise an oral carrier at a level of fromabout 5% to about 99%, preferably from about 10% to about 90%, by weightof the compositions. The oral carriers contained in this phase isbroadly described as any material in the oral composition that is not inthe gel network. The oral carrier phase may also be referred to as thebulk phase or solvent phase. The oral carriers are defined broadly toinclude materials, such as abrasive or other non-soluble materials, thatare solids (which may be described by certain analysis as not being in aparticular phase). Oral carriers include cosmetic or therapeutic activesand non-actives materials.

Oral carriers suitable for the preparation of oral composition are wellknown. Their selection will depend on secondary considerations liketaste, cost, stability, benefits desired, etc.

1. Cosmetic or Therapeutic Actives

The dentifrice composition may also comprise suitable cosmetic and/ortherapeutic actives. Such actives include any material that is generallyconsidered safe for use in the oral cavity and that provides changes tothe overall appearance and/or health of the oral cavity, including, butnot limited to, anti-calculus agents, fluoride ion sources, stannous ionsources, whitening agents, anti-microbial, anti-plaque agents,anti-inflammatory agents, nutrients, antioxidants, anti-viral agents,analgesic and anesthetic agents, H-2 antagonists, and mixture thereof.When present, the level of cosmetic and/or therapeutic active in theoral composition is, in one embodiment from about 0.001% to about 90%,in another embodiment from about 0.01% to about 50%, and in anotherembodiment from about 0.1% to about 30%, by weight of the oralcomposition.

The following is a non-limiting list of actives that may be used in thepresent invention.

a) Fluoride Ion

The present invention comprises a safe and effective amount of afluoride compound (e.g. water soluble). The fluoride ion is present inan amount sufficient to give a fluoride ion concentration in thecomposition at 25° C., and/or in one embodiment can be used at levels offrom about 0.0025% to about 5.0% by weight, in another embodiment fromabout 0.005% to about 2.0% by weight, to provide anticarieseffectiveness. A wide variety of fluoride ion-yielding materials can beemployed as sources of soluble fluoride in the present compositions.Examples of suitable fluoride ion-yielding materials are disclosed inU.S. Pat. Nos. 3,535,421, and 3,678,154. Representative fluoride ionsources include: stannous fluoride, sodium fluoride, potassium fluoride,amine fluoride, sodium monofluorophosphate and many others. In oneembodiment the dentifrice composition comprises stannous fluoride orsodium fluoride, as well as mixtures thereof.

b) Anticalculus Agent

Dentifrice compositions of the present invention may also comprise ananti-calculus agent, which in one embodiment may be present from about0.05% to about 50%, by weight of the dentifrice composition, in anotherembodiment is from about 0.05% to about 25%, and in another embodimentis from about 0.1% to about 15%. The anti-calculus agent may be selectedfrom the group consisting of polyphosphates (including pyrophosphates)and salts thereof; polyamino propane sulfonic acid (AMPS) and saltsthereof; polyolefin sulfonates and salts thereof; polyvinyl phosphatesand salts thereof; polyolefin phosphates and salts thereof;diphosphonates and salts thereof; phosphonoalkane carboxylic acid andsalts thereof; polyphosphonates and salts thereof; polyvinylphosphonates and salts thereof; polyolefin phosphonates and saltsthereof; polypeptides; and mixtures thereof. In one embodiment, thesalts are alkali metal salts. Polyphosphates are generally employed astheir wholly or partially neutralized water-soluble alkali metal saltssuch as potassium, sodium, ammonium salts, and mixtures thereof. Theinorganic polyphosphate salts include alkali metal (e.g. sodium)tripolyphosphate, tetrapolyphosphate, dialkyl metal (e.g. disodium)diacid, trialkyl metal (e.g. trisodium) monoacid, potassium hydrogenphosphate, sodium hydrogen phosphate, and alkali metal (e.g. sodium)hexametaphosphate, and mixtures thereof. Polyphosphates larger thantetrapolyphosphate usually occur as amorphous glassy materials. In oneembodiment the polyphosphates are those manufactured by FMC Corporation,which are commercially known as Sodaphos (n≈6), Hexaphos (n≈13), andGlass H (n≈21, sodium hexametaphosphate), and mixtures thereof. Thepyrophosphate salts useful in the present invention include, alkalimetal pyrophosphates, di-, tri-, and mono-potassium or sodiumpyrophosphates, dialkali metal pyrophosphate salts, tetraalkali metalpyrophosphate salts, and mixtures thereof. In one embodiment thepyrophosphate salt is selected from the group consisting of trisodiumpyrophosphate, disodium dihydrogen pyrophosphate (Na₂H₂P₂O₇),dipotassium pyrophosphate, tetrasodium pyrophosphate (Na₄P₂O₇),tetrapotassium pyrophosphate (K₄P₂O₇), and mixtures thereof. Polyolefinsulfonates include those wherein the olefin group contains 2 or morecarbon atoms, and salts thereof. Polyolefin phosphonates include thosewherein the olefin group contains 2 or more carbon atoms.Polyvinylphosphonates include polyvinylphosphonic acid. Diphosphonatesand salts thereof include azocycloalkane-2,2-diphosphonic acids andsalts thereof, ions of azocycloalkane-2,2-diphosphonic acids and saltsthereof, azacyclohexane-2,2-diphosphonic acid,azacyclopentane-2,2-diphosphonic acid,N-methyl-azacyclopentane-2,3-diphosphonic acid, EHDP(ethane-1-hydroxy-1,1,-diphosphonic acid), AHP(azacycloheptane-2,2-diphosphonic acid),ethane-1-amino-1,1-diphosphonate, dichloromethane-diphosphonate, etc.Phosphonoalkane carboxylic acid or their alkali metal salts include PPTA(phosphonopropane tricarboxylic acid), PBTA(phosphonobutane-1,2,4-tricarboxylic acid), each as acid or alkali metalsalts. Polyolefin phosphates include those wherein the olefin groupcontains 2 or more carbon atoms. Polypeptides include polyaspartic andpolyglutamic acids.

c) Stannous Ion

The dentifrice compositions of the present invention may include astannous ion source. The stannous ions may be provided from stannousfluoride and/or other stannous salts. Stannous fluoride has been foundto help in the reduction of gingivitis, plaque, sensitivity, and inimproved breath benefits. The stannous ions provided in a dentifricecomposition will provide efficacy to a subject using the dentifricecomposition. Although efficacy could include benefits other than thereduction in gingivitis, efficacy is defined as a noticeable amount ofreduction in situ plaque metabolism. Formulations providing suchefficacy typically include stannous levels provided by stannous fluorideand/or other stannous salts ranging from about 3,000 ppm to about 15,000ppm stannous ions in the total dentifrice composition. The stannous ionis present in an amount of from about 4,000 ppm to about 12,000 ppm, inone embodiment from about 5,000 ppm to about 10,000 ppm. Other stannoussalts include organic stannous carboxylates, such as stannous acetate,stannous gluconate, stannous oxalate, stannous malonate, stannouscitrate, stannous ethylene glycoxide, stannous formate, stannoussulfate, stannous lactate, stannous tartrate, and the like. Otherstannous ion sources include, stannous halides such as stannouschlorides, stannous bromide, stannous iodide and stannous chloridedihydride. In one embodiment the stannous ion source is stannousfluoride in another embodiment, stannous chloride dihydrate. Thecombined stannous salts may be present in an amount of from about 0.001%to about 11%, by weight of the dentifrice compositions. The stannoussalts may, in one embodiment, be present in an amount of from about0.01% to about 7%, in another embodiment from about 0.1% to about 5%,and in another embodiment from about 1.5% to about 3%, by weight of thedentifrice composition.

d) Whitening Agent

A whitening agent may be included as an active in the present dentifricecompositions. The actives suitable for whitening are selected from thegroup consisting of alkali metal and alkaline earth metal peroxides,metal chlorites, perborates inclusive of mono and tetrahydrates,perphoshates, percarbonates, peroxyacids, and persulfates, such asammonium, potassium, sodium and lithium persulfates, and combinationsthereof. Suitable peroxide compounds include hydrogen peroxide, ureaperoxide, calcium peroxide, carbamide peroxide, magnesium peroxide, zincperoxide, strontium peroxide and mixtures thereof. In one embodiment theperoxide compound is carbamide peroxide. Suitable metal chloritesinclude calcium chlorite, barium chlorite, magnesium chlorite, lithiumchlorite, sodium chlorite, and potassium chlorite. Additional whiteningactives may be hypochlorite and chlorine dioxide. In one embodiment thechlorite is sodium chlorite. In another embodiment the percarbonate issodium percarbonate. In one embodiment the persulfates are oxones. Thelevel of these substances is dependent on the available oxygen orchlorine, respectively, that the molecule is capable of providing tobleach the stain. In one embodiment the whitening agents may be presentat levels from about 0.01% to about 40%, in another embodiment fromabout 0.1% to about 20%, in another embodiment form about 0.5% to about10%, and in another embodiment from about 4% to about 7%, by weight ofthe dentifrice composition. The gel network composition may contain awhitening agent or peroxide or it may be contained in the oral carrierphase. The gel network may aid in the stabilizing of peroxides.

e) Anti-Microbial Agent

Anti-microbial agents may be included in the dentifrice compositions ofthe present invention. Such agents may include, but are not limited to:5-chloro-2-(2,4-dichlorophenoxy)-phenol, commonly referred to astriclosan; 8-hydroxyquinoline and its salts; copper II compounds,including, but not limited to, copper(II) chloride, copper(II) sulfate,copper(II) acetate, copper(II) fluoride and copper(II) hydroxide;phthalic acid and its salts including, but not limited to thosedisclosed in U.S. Pat. No. 4,994,262, including magnesium monopotassiumphthalate; chlorhexidine; alexidine; hexetidine; sanguinarine;benzalkonium chloride; salicylanilide; domiphen bromide; cetylpyridiniumchloride (CPC); tetradecylpyridinium chloride (TPC);N-tetradecyl-4-ethylpyridinium chloride (TDEPC); octenidine; iodine;sulfonamides; bisbiguanides; phenolics; delmopinol, octapinol, and otherpiperidino derivatives; niacin preparations; zinc or stannous ionagents; nystatin; grapefruit extract; apple extract; thyme oil; thymol;antibiotics such as augmentin, amoxicillin, tetracycline, doxycycline,minocycline, metronidazole, neomycin, kanamycin, cetylpyridiniumchloride, and clindamycin; analogs and salts of the above; methylsalicylate; hydrogen peroxide; metal salts of chlorite; and mixtures ofall of the above. Anti-microbial components may be present from about0.001% to about 20% by weight of the dentifrice composition. In anotherembodiment the antimicrobial agents generally comprise from about 0.1%to about 5% by weight of the dentifrice compositions of the presentinvention.

f) Anti-Plaque Agent

The dentifrice compositions of the present invention may include ananti-plaque agent such as stannous salts, copper salts, strontium salts,magnesium salts or a dimethicone copolyol. The dimethicone copolyol isselected from C12 to C20 alkyl dimethicone copolyols and mixturesthereof. In one embodiment the dimethicone copolyol is cetyl dimethiconecopolyol marketed under the Trade Name Abil EM90. The dimethiconecopolyol in one embodiment can be present in a level of from about0.001% to about 25%, in another embodiment from about 0.01% to about 5%,and in another embodiment from about 0.1% to about 1.5% by weight of thedentifrice composition.

g) Anti-Inflammatory Agent

Anti-inflammatory agents can also be present in the dentifricecompositions of the present invention. Such agents may include, but arenot limited to, non-steroidal anti-inflammatory (NSAID) agents oxicams,salicylates, propionic acids, acetic acids and fenamates. Such NSAIDsinclude but are not limited to ketorolac, flurbiprofen, ibuprofen,naproxen, indomethacin, diclofenac, etodolac, indomethacin, sulindac,tolmetin, ketoprofen, fenoprofen, piroxicam, nabumetone, aspirin,diflunisal, meclofenamate, mefenamic acid, oxyphenbutazone,phenylbutazone and acetaminophen. Use of NSAIDs such as ketorolac areclaimed in U.S. Pat. No. 5,626,838. Disclosed therein are methods ofpreventing and/or treating primary and reoccurring squamous cellcarcinoma of the oral cavity or oropharynx by topical administration tothe oral cavity or oropharynx of an effective amount of an NSAID.Suitable steroidal anti-inflammatory agents include corticosteroids,such as fluccinolone, and hydrocortisone.

h) Nutrients

Nutrients may improve the condition of the oral cavity and can beincluded in the dentifrice compositions of the present invention.Nutrients include minerals, vitamins, oral nutritional supplements,enteral nutritional supplements, and mixtures thereof. Useful mineralsinclude calcium, phosphorus, zinc, manganese, potassium and mixturesthereof. Vitamins can be included with minerals or used independently.Suitable vitamins include Vitamins C and D, thiamine, riboflavin,calcium pantothenate, niacin, folic acid, nicotinamide, pyridoxine,cyanocobalamin, para-aminobenzoic acid, bioflavonoids, and mixturesthereof. Oral nutritional supplements include amino acids, lipotropics,fish oil, and mixtures thereof. Amino acids include, but are not limitedto L-Tryptophan, L-Lysine, Methionine, Threonine, Levocarnitine orL-camitine and mixtures thereof. Lipotropics include, but are notlimited to, choline, inositol, betaine, linoleic acid, linolenic acid,and mixtures thereof. Fish oil contains large amounts of Omega-3 (N-3)polyunsaturated fatty acids, eicosapentaenoic acid and docosahexaenoicacid. Enteral nutritional supplements include, but are not limited to,protein products, glucose polymers, corn oil, safflower oil, mediumchain triglycerides. Minerals, vitamins, oral nutritional supplementsand enteral nutritional supplements are described in more detail in DrugFacts and Comparisons (loose leaf drug information service), WoltersKluer Company, St. Louis, Mo., © 1997, pps. 3-17 and 54-57.

i) Antioxidants

Antioxidants are generally recognized as useful in dentifricecompositions. Antioxidants are disclosed in texts such as Cadenas andPacker, The Handbook of Antioxidants, © 1996 by Marcel Dekker, Inc.Antioxidants useful in the present invention include, but are notlimited to, Vitamin E, ascorbic acid, Uric acid, carotenoids, Vitamin A,flavonoids and polyphenols, herbal antioxidants, melatonin,aminoindoles, lipoic acids and mixtures thereof.

j) Analgesic and Anesthetic Agents

Anti-pain or desensitizing agents can also be present in the dentifricecompositions of the present invention. Analgesics are agents thatrelieve pain by acting centrally to elevate pain threshold withoutdisturbing consciousness or altering other sensory modalities. Suchagents may include, but are not limited to: strontium chloride;potassium nitrate; sodium fluoride; sodium nitrate; acetanilide;phenacetin; acertophan; thiorphan; spiradoline; aspirin; codeine;thebaine; levorphenol; hydromorphone; oxymorphone; phenazocine;fentanyl; buprenorphine; butaphanol; nalbuphine; pentazocine; naturalherbs, such as gall nut; Asarum; Cubebin; Galanga; scutellaria;Liangmianzhen; and Baizhi. Anesthetic agents, or topical analgesics,such as acetaminophen, sodium salicylate, trolamine salicylate,lidocaine and benzocaine may also be present. These analgesic activesare described in detail in Kirk-Othmer, Encyclopedia of ChemicalTechnology, Fourth Edition, Volume 2, Wiley-Interscience Publishers(1992), pp. 729-737.

k) H-1 and H-2 Antagonists

The present invention may also optionally comprise selective H-1 and H-2antagonists including compounds disclosed in U.S. Pat. No. 5,294,433.

1) Antiviral Actives

Antiviral actives useful in the present composition include any knowactives that are routinely use to treat viral infections. Suchanti-viral actives are disclosed in Drug Facts and Comparisons, WoltersKluer Company, © 1997, pp. 402(a)-407(z). Specific examples includeanti-viral actives disclosed in U.S. Pat. No. 5,747,070, issued May 5,1998. Said Patent discloses the use of stannous salts to controlviruses. Stannous salts and other anti-viral actives are described indetail in Kirk & Othmer, Encyclopedia of Chemical Technology, ThirdEdition, Volume 23, Wiley-Interscience Publishers (1982), pp. 42-71. Thestannous salts that may be used in the present invention would includeorganic stannous carboxylates and inorganic stannous halides. Whilestannous fluoride may be used, it is typically used only in combinationwith another stannous halide or one or more stannous carboxylates oranother therapeutic agent.

m) Chelant

Chelating agents are able to complex calcium found in the cell walls ofbacteria and can help to disrupt plaque by removing calcium from thecalcium bridges which help hold this biomass intact. Suitable chelatingagents include tartaric acid and salts thereof, citric acid and alkalimetal citrates, soluble pyrophosphates, anionic polymericpolycarboxylates, and combinations thereof.

n) Anti-erosion Agents

The present compositions optionally contain anti-erosion agents such asdescribed in commonly-assigned U.S. Pat. No. 6,685,920. Dental erosionis a permanent loss of tooth substance from the surface by the action ofchemicals, such as harsh abrasives and acids, as opposed to subsurfacedemineralization or caries caused by bacterial action. Anti-erosionagents described therein have affinity for the tooth surface. Theseagents either bind to the tooth surface or form insoluble compounds orcomplexes on the tooth surface, thereby forming a protective film orcoating on the tooth surface. As a result of these protective coatings,teeth are provided with remarkable resistance and protection againstdental erosion challenges for extended periods of time following use ofthe composition containing these agents. Useful anti-erosion agentsinclude polymeric mineral surface active agents such as condensedphosphorylated polymers; polyphosphonates; polycarboxylates andcarboxy-substituted polymers; copolymers of phosphate- orphosphonate-containing monomers or polymers with ethylenicallyunsaturated monomers, amino acids, or with other polymers selected fromproteins, polypeptides, polysaccharides, poly(acrylate),poly(acrylamide), poly(methacrylate), poly(ethacrylate),poly(hydroxyalkylmethacrylate), poly(vinyl alcohol), poly(maleicanhydride), poly(maleate) poly(amide), poly(ethylene amine),poly(ethylene glycol), poly(propylene glycol), poly(vinyl acetate) orpoly(vinyl benzyl chloride); and mixtures thereof. Also useful asanti-erosion agents are metal ions selected from stannous, zinc andcopper, which deposit onto teeth a highly insoluble film or precipitateof compounds or complexes formed from the reaction of the metal ionswith other ingredients of the oral composition and/or components of theenamel surface.

o) Additional Actives

Additional actives suitable for use in the present invention mayinclude, but are not limited to, insulin, steroids, natural materials,herbal and other plant derived remedies. Additionally, anti-gingivitisor gum care agents known in the art may also be included. Componentswhich impart a clean feel to the teeth may optionally be included. Thesecomponents may include, for example, baking soda or Glass-H. Also, it isrecognized that in certain forms of therapy, combinations of theseabove-named agents may be useful in order to obtain an optimal effect.Thus, for example, an anti-microbial and an anti-inflammatory agent maybe combined in a single dentifrice composition to provide combinedeffectiveness. Other ingredients, such as materials providinganti-sensitivity benefits, may also be used.

Optional agents to be used include such known materials as syntheticanionic polymers, including polyacrylates and copolymers of maleicanhydride or acid and methyl vinyl-ether (e.g., Gantrez), as described,for example, in U.S. Pat. No. 4,627,977, as well as, e.g., polyaminopropoane sulfonic acid (AMPS), zinc citrate trihydrate, polyphosphates(e.g., tripolyphosphate; hexametaphosphate), diphosphonates (e.g., EHDP;AHP), polypeptides (such as polyaspartic and polyglutamic acids), andmixtures thereof. Additionally, the dentifrice composition can include apolymer carrier, such as those described in U.S. Pat. Nos. 6,682,722 and6,589,512 and U.S. application Ser. Nos. 10/424,640 and 10/430,617.

2. Additional Oral Carriers

a) Buffering Agents

The oral compositions may contain a buffering agent. Buffering agents,as used herein, refer to agents that can be used to adjust the pH of theoral compositions to a range of about pH 3.0 to about pH 10. Thebuffering agents include alkali metal hydroxides, ammonium hydroxide,organic ammonium compounds, carbonates, sesquicarbonates, borates,silicates, phosphates, imidazole, and mixtures thereof. Specificbuffering agents include monosodium phosphate, trisodium phosphate,sodium benzoate, benzoic acid, sodium hydroxide, potassium hydroxide,alkali metal carbonate salts, sodium carbonate, imidazole, pyrophosphatesalts, citric acid, and sodium citrate. Buffering agents are used at alevel of from about 0.1% to about 30%, preferably from about 0.1% toabout 10%, and more preferably from about 0.3% to about 3%, by weight ofthe oral composition.

b) Abrasive Polishing Materials

An abrasive polishing material may also be included in the oralcompositions. The abrasive polishing material contemplated for use inthe compositions of the present invention can be any material that doesnot excessively abrade dentin. Typical abrasive polishing materialsinclude silicas including gels and precipitates; aluminas; phosphatesincluding orthophosphates, polymetaphosphates, and pyrophosphates; andmixtures thereof. Specific examples include dicalcium orthophosphatedihydrate, calcium pyrophosphate, tricalcium phosphate, calciumpolymetaphosphate, insoluble sodium polymetaphosphate, rice hull silica,hydrated alumina, beta calcium pyrophosphate, calcium carbonate, andresinous abrasive materials such as particulate condensation products ofurea and formaldehyde, and others such as disclosed by Cooley et al inU.S. Pat. No. 3,070,510, issued Dec. 25, 1962. Mixtures of abrasives mayalso be used. If the oral composition or particular phase comprises apolyphosphate having an average chain length of about 4 or more, calciumcontaining abrasives and alumina are not preferred abrasives. The mostpreferred abrasive is silica.

Silica dental abrasives of various types are preferred because of theirunique benefits of exceptional dental cleaning and polishing performancewithout unduly abrading tooth enamel or dentine. The silica abrasivepolishing materials herein, as well as other abrasives, generally havean average particle size ranging between about 0.1 to about 30 microns,and preferably from about 5 to about 15 microns. The abrasive can beprecipitated silica or silica gels such as the silica xerogels describedin Pader et al., U.S. Pat. No. 3,538,230, issued Mar. 2, 1970, andDiGiulio, U.S. Pat. No. 3,862,307, issued Jan. 21, 1975. Preferred arethe silica xerogels marketed under the trade name “Syloid” by the W. R.Grace & Company, Davison Chemical Division. Also preferred are theprecipitated silica materials such as those marketed by the J. M. HuberCorporation under the trade name, “Zeodent”, particularly the silicacarrying the designation “Zeodent 119.” The types of silica dentalabrasives useful in the toothpastes of the present invention aredescribed in more detail in Wason, U.S. Pat. No. 4,340,583, issued Jul.29, 1982. Silica abrasives are also described in Rice, U.S. Pat. Nos.5,589,160; 5,603,920; 5,651,958; 5,658,553; and 5,716,601. The abrasivein the oral compositions described herein is generally present at alevel of from about 6% to about 70% by weight of the composition.Preferably, oral compositions contain from about 10% to about 50% ofabrasive, by weight of the oral composition.

c) Titanium Dioxide

Titanium dioxide may also be added to the present composition. Titaniumdioxide is a white powder which adds opacity to the compositions.Titanium dioxide generally comprises from about 0.25% to about 5%, byweight of the composition.

d) Coloring Agents

Coloring agents may also be added to the present composition. Thecoloring agent may be in the form of an aqueous solution, preferably 1%coloring agent in a solution of water. Pigments, pealing agents, fillerpowders, talc, mica, magnesium carbonate, calcium carbonate, bismuthoxychloride, zinc oxide, and other materials capable of creating avisual change to the oral compositions may also be used. Color solutionsand other agents generally comprise from about 0.01% to about 5%, byweight of the composition.

e) Flavoring Components

Suitable flavoring components include oil of wintergreen, clove bud oil,menthol, anethole, methyl salicylate, eucalyptol, cassia, 1-menthylacetate, sage, eugenol, parsley oil, oxanone, alpha-irisone, marjoram,lemon, orange, propenyl guaethol, cinnamon, vanillin, ethyl vanillin,heliotropine, 4-cis-heptenal, diacetyl, methyl-para-tert-butyl phenylacetate, cranberry, chocolate, green tea, and mixtures thereof. Coolantsmay also be part of the flavor composition. Coolants suitable for thepresent compositions include the paramenthan carboxyamide agents such asN-ethyl-p-menthan-3-carboxamide (known commercially as WS-3, WS-23,WS-5), MGA, TK-10, Physcool, and mixtures thereof. Salivating agents,warming agents, numbing agents, and other optional materials can be usedto deliver a signal while the oral composition is being used. A flavorcomposition is generally used in the oral care compositions at levels offrom about 0.001% to about 5%, by weight of the oral care composition.The flavor composition will preferably be present in an amount of fromabout 0.01% to about 4%, more preferably from about 0.1% to about 3%,and more preferably from about 0.5% to about 2% by weight.

f) Sweetening Agents

Sweetening agents can be added to the compositions. These includesaccharin, dextrose, sucrose, lactose, xylitol, maltose, levulose,aspartame, sodium cyclamate, D-tryptophan, dihydrochalcones, acesulfame,sucralose, neotame, and mixtures thereof. Various coloring agents mayalso be incorporated in the present invention. Sweetening agents aregenerally used in toothpastes at levels of from about 0.005% to about5%, by weight of the composition.

g) Thickening Agents

Although the oral composition of the present invention is structured orthickened by the gel network, additional thickening agents, such aspolymeric thickeners, may be utilized. In some embodiment, the majorityof the structuring of the oral composition is from the gel network. Inother embodiment, the majority of the structuring may be from apolymeric thickening agent with the gel network providing additionalstructuring to the oral composition.

Suitable thickening agents are carboxyvinyl polymers, carrageenan,hydroxyethyl cellulose, laponite and water soluble salts of celluloseethers such as sodium carboxymethylcellulose and sodium carboxymethylhydroxyethyl cellulose. Natural gums such as gum karaya, xanthan gum,gum arabic, and gum tragacanth can also be used. Colloidal magnesiumaluminum silicate or finely divided silica can be used as part of thethickening agent to further improve texture. Thickening agents caninclude polymeric polyether compounds, e.g., polyethylene orpolypropylene oxide (M. W. 300 to 1,000,000), capped with alkyl or acylgroups containing 1 to about 18 carbon atoms.

A suitable class of thickening or gelling agents includes a class ofhomopolymers of acrylic acid crosslinked with an alkyl ether ofpentaerythritol or an alkyl ether of sucrose, or carbomers. Carbomersare commercially available from B. F. Goodrich as the Carbopol® series.Particularly the carbopols include Carbopol 934, 940, 941, 956, andmixtures thereof.

Copolymers of lactide and glycolide monomers, the copolymer having themolecular weight in the range of from about 1,000 to about 120,000(number average), are useful for delivery of actives into theperiodontal pockets or around the periodontal pockets as a “subgingivalgel carrier.” These polymers are described in U.S. Pat. Nos. 5,198,220;5,242,910; and 4,443,430.

Thickening agents in an amount from about 0% to about 15%, or from about0.01% to about 6%, in another embodiment from about 0.1% to about 5%, byweight of the total oral composition, can be used. The oral compositioncan be essentially free of thickening agents if it is structured orthickened by the gel network. In other embodiments, a small amount of athickening agent, such as from about 0.01% to about 1% or from about0.05% to about 0.5%, can be used in combination with the gel network.The specific amount of thickening agent will be selected based on thedesired rheology and function of the gel network.

h) Humectant

A humectant can help to keep the dentifrice composition from hardeningupon exposure to air and provide a moist feel in the mouth. A solvent isrequired in the gel network phase. A humectant or additional solvent maybe added to the oral carrier phase. Suitable humectants for the presentinvention include water, edible polyhydric alcohols such as glycerin,sorbitol, xylitol, butylene glycol, polyethylene glycol, propyleneglycol, and combinations thereof. Sorbitol, glycerin, water, andcombinations thereof are preferred humectants. The humectant may bepresent in an amount of from about 0.1% to about 99% , from about 0.5%to about 95%, and from about 1% to about 90%. The oral carrier phase canalso be made without a humectant. The oral composition structured with agel network instead of typical polyermic thickener, or with low levelsof polymeric thickeners, may not require a humectant or may allow forlower levels of humectants. The oral composition with the gel networkwill typically provide a moist mouthfeel and/or not become dried outwhen exposed to air. A gel network composition could be free ofhumectants or anhydrous for use as a denture adhesive composition.

i) Sufactants

An additional surfactant may be added to the oral carrier phase of theoral composition. This may be the same surfactant that is added to thegel network phase or a different surfactant. A surfactant may aid in thecleaning or foaming of the oral composition. Suitable surfactants aredescribed above in the gel network section.

C. Process of Making an Oral Composition

An aspect of the invention relates to a process of making an oralcomposition of the present invention. The process of making an oralcomposition comprises (a) heating the fatty amphiphile, a secondarysurfactant, and solvent to a temperature sufficient to allowpartitioning of the secondary surfactant and the solvent into the fattyamphiphile, typically at least about 5° C. above the melt temperature ofthe fatty amphiphile, and (b) cooling the pre-mix below the melttemperature of the fatty amphiphile to form a gel network. The oralcarrier ingredients may be added at any time during the process such asbefore heating, during heating, before cooling, or after cooling. It maybe desired to add certain oral carrier ingredients after heating, suchas the flavor.

In one embodiment of the present invention, the gel network phase of thepresent invention may be prepared by heating the fatty amphiphile, thesecondary surfactant, and solvent to a level of at least 5° C. above themelt temperature of the fatty amphiphile. The heating may be in therange of about 50° C. to about 90° C., typically from about 70° C. toabout 90° C. Preferably, the materials are before heating, duringheating, after heating, during cooling, and after cooling. After beingheated, the mixture is cooled to a level in the range of about 20° C. toabout 35° C. Depending upon the size of the batch, equipment, specificmaterials, and time, the mixture may be cooled by mixing only, by an icebath, or by passing the mixture through a heat exchanger. As a result ofthis cooling step, the fatty amphiphile and the secondary surfactantcrystallize to form a crystalline gel network.

Alternative methods of preparing the gel network component includesonication and/or milling of the fatty amphiphile, the secondarysurfactant, and solvent, while these components are heated, to reducethe particle size of the melted fatty amphiphile phase. This results inan increase in surface area of the fatty amphiphile phase, which allowsthe secondary surfactant and the solvent to swell the fatty amphiphilephase. Another suitable variation in preparing the gel network includesheating and mixing the fatty amphiphile and the secondary surfactantfirst, and then adding that mixture to the solvent.

The gel network can be used by itself to structure or thicken the oralcomposition to provide the desired rheology. The gel network can also beused in combination with other thickening materials. The gel network maybe formulated to produce a dentifrice: having rheology enabling thesolids and other particles to be suspended, easily dispensed from acontainer, stand-up on a toothbrush head once the dentifrice isdispensed, low or no stringiness when dispensed, ease of dispersion inthe mouth, and other rheological properties desired of a dentifrice.

The viscosity of the dentifrice is typically from about 8 to about 100BKU, from about 15 to about 80 BKU, and commonly from about 15 to about50 BKU. As used herein, BKU is the unit of viscosity. The viscometer isBrookfield viscometer, Model ½ RVT (½ spring strength), with aBrookfield “Helipath” stand. The spindle is a conventional “E-series”T-shaped spindle. The viscometer is placed on the Helipath stand andleveled via spirit levels. The E spindle is attached, and the viscometeris set to 2.5 RPM while it is running. The viscosity is measured after 1minute and the temperature is constant at 25° C. The dentifricecomposition will have an acceptable rheology, good texture, pleasingaesthetics, and a deaerated specific gravity from about 0.9 to about 1.8and can be from about 1.1 to about 1.6.

D. Method of Use

The compositions of the present invention are used in a conventionalmanner for cleansing the teeth. Generally, a method of using adentifrice to cleanse the teeth comprises applying the composition ofthe present invention to a toothbrush, brushing the teeth for a periodof time, and then rinsing the dentifrice from the mouth. From about 0.01to about 3 grams of toothpaste is typically used.

NON-LIMITING EXAMPLES

The oral compositions illustrated in the following Examples illustratespecific embodiments of the oral compositions of the present invention,but are not intended to be limiting thereof. Other modifications can beundertaken by the skilled artisan without departing from the spirit andscope of this invention.

Oral Composition Examples

The following Examples illustrate specific embodiments of the oralcomposition utilizing gel networks.

In examples 1-4, a gel network is formed in Step 1 and then other oralcarriers are added to the gel network. For examples 1-4, Step 1ingredients are combined in a mixing vessel and heated to between about75° C. to about 90° C. while being mixed. The mixture is further mixedand then cooled to about 25° C. to form a crystalline gel network. Oncethe gel network is formed, the Step 2 ingredient are added eitherindividually or a premix and mixed to form the oral composition. As istypical, the flavor is added as the final ingredient to minimizevolatile loss.

Examples 1-4

Premix Ingredients Example 1 Example 2 Example 3 Example 4 1 Water31.15% 25.70%  31.88% 1 Glycerin (@99.7%) 38.00% 69.45% 44.00% 1Sorbitol (@ 70%) 20.0% 1 Sodium Lauryl Sulfate 3.00% 3.50% 5.00% 7.00%(@28%) 1 Cetyl Alcohol 1.90% 1.50% 3.00% 2.20% 1 Stearyl Alcohol 1.90%1.50% 3.00% 2.20% 2 Sodium Fluoride 0.24% 0.24% 0.24% 2 DisodiumMonoFluoro 0.80% Phosphate (MFP) 2 Calcium Carbonate 40.00%  (groundlimestone 2531) 2 Silica 17.00% 17.00% 5.00% 2 Sodium Acid 1.00% 1.00%Pyrophosphate 2 Tetra Sodium 3.85% 3.85% 1.00% 6.00% Pyrophosphate 2Sodium Saccharin 0.46% 0.46% 0.50% 0.48% 2 Titanium Dioxide 0.50% 0.50%Peppermint Flavor 1.00% 1.00% 1.00% 1.00%

In examples 5-14, the gel network is formed as the oral composition ismade. All of the materials listed in Examples 5-14 can be added at anytime as long as the fatty amphiphile, secondary surfactant, and solventneeded to make the gel network are added prior to the heating step andcooling step. In these embodiments, the flavor is also added as thefinal ingredient.

Examples 5-9

Ingredients Example 5 Example 6 Example 7 Example 8 Example 9 Water qsqs Qs qs qs Sorbitol (@ 70%) 50.00% 50.00% 50.00% 50.00% 50.00%Cocamidopropyl 4.00% Betaine (@ 30%) Sodium Alkyl 2.53% C10-16 GlycerylSulfonate (@47.5%) Sarcosinate LN30 4.00% (@ 30%) Sodium Methyl 4.00%Cocoyl Taurate (@ 30%) Cetyl Pyridinium 1.20% Chloride Cetyl Alcohol2.00% 2.00% 2.00% 2.00% 2.00% Stearyl Alcohol 2.00% 2.00% 2.00% 2.00%2.00% Sodium Fluoride 0.24% 0.24% 0.24% 0.24% 0.24% Silica 17.00% 17.00%17.00% 17.00% 17.00% Sodium Acid 1.00% 1.00% 1.00% 1.00% 1.00%Pyrophosphate Tetra Sodium 3.85% 3.85% 3.85% 3.85% 3.85% PyrophosphateSodium Saccharin 0.46% 0.46% 0.46% 0.46% 0.46% Titanium Dioxide 0.50%0.50% 0.50% 0.50% 0.50% Peppermint Flavor 1.00% 1.00% 1.00% 1.00% 1.00%

Examples 10-14

Example Example Example Example Example Ingredients 10 11 12 13 14 Waterqs qs qs qs qs Sorbitol (@ 70%) 50.00% 50.00% 50.00% 50.00% 50.00%Sodium Lauryl 2.00% 4.00% 4.00% 4.00% 4.00% Sulfate (@ 28%)Cocamidopropyl 2.00% Betaine (@ 30%) Cetyl Alcohol 2.00% 1.50% 1.50%1.50% Stearyl Alcohol 2.00% 1.00% 1.50% 1.50% 1.50% Behenyl Alcohol2.50% (Lanette-22) Carboxy Methyl Cellulose 0.50% Xanthan gum(Keltrol-F) 0.50% Iota Carrageenan 0.50% Sodium Fluoride 0.24% 0.24%0.24% 0.24% 0.24% Silica 17.00% 17.00% 17.00% 17.00% 17.00% Sodium Acid1.00% 1.00% 1.00% 1.00% 1.00% Pyrophosphate Tetra Sodium 3.85% 3.85%3.85% 3.85% 3.85% Pyrophosphate Sodium Saccharin 0.46% 0.46% 0.46% 0.46%0.46% Titanium Dioxide 0.50% 0.50% 0.50% 0.50% 0.50% Peppermint Flavor1.00% 1.00% 1.00% 1.00% 1.00%

In Examples 15-18, the gel network is formed in Step 1 and the otheringredients added as Step 2 with the flavor added last when the batch iscool.

Examples 15-18

Example Example Example Example Step Ingredients 15 16 17 18 1 Water Qsqs qs qs 1 Sorbitol (@ 70%)   50%   50%   50%   50% 1 Phospholipid 1.50%2.50% PTM (@30%) 1 Sodium Lauryl 2.50% 1.50% Sulfate (@28%) 1 CetylAlcohol 3.00% 2.00% 2.00% 2.00% 1 Stearyl Alcohol 3.00% 2.00% 2.00%2.00% 2 Sodium Fluoride 0.24% 0.24% 0.24% 0.24% 2 Sodium Lauroyl 2.00%2.00% Glutamate (@30%) 2 Cetyl Betaine 2.50% 2.50% 2 Silica 17.00% 17.00%  17.00%  17.00%  2 Sodium Acid 1.00% 1.00% 1.00% 1.00%Pyrophosphate 2 Tetra Sodium 3.85% 3.85% 3.85% 3.85% Pyrophosphate 2Sodium Saccharin 0.46% 0.46% 0.46% 0.46% 2 Titanium Dioxide 0.50% 0.50%0.50% 0.50% Peppermint 1.00% 1.00% 1.00% 1.00% Flavor

In other examples, a concentrated dentifrice may be formed. Theconcentrated dentifrice is structured by a gel network. After packaging,a solvent, preferably water, could be added to the concentrateddentifrice to form dentifrice with typical levels of actives andrheology for brushing. An oral care composition structured by a gelnetwork retains a homogeneous structure when diluted with excess amountsof water or other solvents. This is in contrast to typical polymerthickened oral compositions. The concentrated dentifrice may beformulated to contain twice, three times, four times, five times, ormore of the amount of active or solid materials as in typical dentifricecompositions. The concentrated dentifrice can be diluted prior to use orduring use.

More than one gel network composition may be used in an oralcomposition. Two or more gel network compositions can be used tostructure the oral composition. Alternatively, one gel networkcomposition can be used to structure the oral composition and a secondgel network to aid in the delivery of a material, such as a flavor. Twoor more gel network compositions may also be desired to achieve certainvisual appearances such as striped or multicolor products. It may bedesired to have more than one gel network composition in an oral carecomposition to provide color stability, flavor delivery, or incorporateincompatible materials. The gel network composition may also aid insequestering flavors or coolants or other large organic materials forvarious types of flavor displays. The gel network composition may alsoaid in the delivery of cationic, anionic, hydrophilic, hydrophobic,insoluble, or soluble materials or combinations thereof. This may bebeneficial in delivering incompatible materials. The gel networkcomposition may also aid in targeting the delivery, release, or extendeddelivery of materials such as actives, flavors, or other materials foraesthetic reasons or other benefits.

Analytical Methods and Examples

The following methods are used to identify gel networks.

Differential Scanning Calorimetry Method

The chain melt temperature of the layer in the gel network comprisingthe one or more fatty amphiphiles (i.e., the melt transition temperaturefor the gel network) may be obtained using differential scanningcalorimetry according to the following method. Utilizing a TAInstruments Q100 DSC, approximately 50 mg of the gel network pre-mix orthe final oral composition containing the gel network is placed into astainless steel high volume DSC pan. The sample, along with an emptyreference pan is placed into the instrument. The samples are analyzedusing the following conditions/temperature program: Nitrogen Purge,Equilibrate @ 5.00° C. until an isothermal is reach for 2.00 min. Rampthe temperature at a rate of 3.00° C./min to 90.00° C. Each sample isanalyzed in duplicate. The resulting DSC data is analyzed using TAInstruments Universal Analysis Software.

The use of DSC to measure the melt transition temperature for gelnetworks is further described by T. de Vringer et al., Colloid andPolymer Science, vol. 265, 448-457 (1987); and H. M. Ribeiro et al.,Intl. J. of Cosmetic Science, vol. 26, 47-59 (2004).

X-Ray Analysis Method

Small-angle x-ray scattering (“SAXS”) as used to resolve periodicstructures in mesophases is essentially an x-ray diffraction technique.It is used in conjunction with conventional wide-angle x-ray diffraction(“WXRD”) to characterize aggregate structures such as micelles, gelnetworks, lamella, hexagonal and cubic liquid crystals. The differentmesophases that show periodic structures can be characterized by therelative positions (d-spacing) of their reflections as derived from theBragg equation (d=λ/2Sin θ) where d represents the interplanar spacing,λ the radiation wavelength and θ the scattering (diffraction) angle.

The one dimensional lamella gel network phase is characterized by theratio of the interplanar spacings d₁/d₁, d₁/d₂, d₁/d₃, d₁/d₄, d₁/d₅having the values 1:2:3:4:5 etc. in the SAXS region (long-range order)and one or two invariant reflection(s) in the WXRD region (short-range)centered around 3.5 and 4.5 Å over a broad halo background. Othermesophases (e.g. hexagonal or cubic) will have characteristicallydifferent d-spacing ratios.

WXRD data are collected in transmission mode on a Stoe STADI-Pdiffractometer equipped with an image plate position-sensitive detector.The specimen is positioned between two milar films in the sample holderand placed in the path of the x-ray beam. The IP detector has a solidangle of about 1200 2°θ and records diffracted x-ray beamssimultaneously. Data are collected and analyzed using the XPOW software.

SAXS data are collected on Rigaku rotating anode generator with a finefocus filament equipped with a HI-STAR 2-dimensional area detector fromBruker-AXS. The setup has an evacuated chamber, which houses thespecimen, conjoined with an evacuated tube leading to the detector toreduce air scatter. The specimen sample holder consists of copper plateswith small rectangular cavities to hold the fluid-like material and alsoallow the transmission of the x-ray beam. The openings to the cavitiesare sealed with kapton windows to provide leak-free environment undervacuum. The 2-D data are azimuthally integrated and reduced to intensityversus scattering vector (q) or its d equivalent by a combination ofGADDS software and in-house software modules implementing knowntechniques on the Igor platform.

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference; the citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention. To the extent that any meaning ordefinition of a term in this written document conflicts with any meaningor definition of the term in a document incorporated by reference, themeaning or definition assigned to the term in this written documentshall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A dentifrice composition comprising: a) a gelnetwork phase comprising: i) from about 0.05% to about 30%, by weight ofthe oral composition of one or more fatty amphiphiles wherein said fattyamphiphile is a combination of cetyl alcohol and stearyl alcohol; ii)from about 0.01% to about 15%, by weight of the composition, of one ormore secondary surfactants having an HLB of 6 or more; and iii) fromabout 0.1% to about 99%, by weight of the composition of one or moresolvents; b) from about 10% to about 90%, by weight of the composition,of an oral carrier phase, wherein the oral carrier phase comprises: i)one or more anionic secondary surfactants selected from sodium laurylsulfate, sodium lauryl sarcosinate, sodium cocoyl methyl taurate, sodiummonoglyceride sulfate, sodium cetaryl sulfate, potassium cocoylglycinate, socium lauryl phosphate, sodium lauryl lactylate, sodiumlauryl sulfoacetate, sodium lauroyl glutamate, sodium laurylisethionate, sodium laureth carboxylate, sodium dodecylbenzenesulfonate, and combinations thereof; ii) a flavoring componentselected from oil of wintergreen, clove bud oil, menthol, anethole,methyl salicylate, eucalyptol, cassia, 1-menthyl acetate, sage, eugenol,parsley oil, oxanone, alpha-irisone, marjoram, lemon, orange, propenylguaethol, cinnamon, vanillin, ethyl vanillin, heliotropine,4-cis-heptenal, diacetyl, methyl-para-tert-butyl phenyl acetate,cranberry, chocolate, green tea, and mixtures thereof; iii) from about0.0025% to about 5.0% by weight of the composition, of a fluoridecompound selected from stannous fluoride or sodium fluoride, as well asmixtures thereof; and iv) from about 10% to about 50%, by weight of thecomposition, of an abrasive polishing material selected from silica,wherein said gel network phase is used to structure said dentifricecomposition; and wherein the weight ratio of the fatty amphiphile to thesurfactant in the gel network component is from greater than about 1:1to about 20:1 wherein the dentifrice composition foams when used in aconventional manner for cleansing teeth.
 2. The dentifrice compositionaccording to claim 1 wherein said secondary surfactant is sodium laurylsulfate.
 3. The dentifrice composition according to claim 1 wherein thedentifrice composition is essentially free of polymeric thickeningmaterials.
 4. The dentifrice composition according to claim 1 whereinthe dentifrice composition comprises a thickening material.
 5. Thedentifrice composition according to claim 1 wherein the gel networkphase provides the dentifrice composition with desired rheology withoutthe use of a polymeric thickening agent.
 6. The dentifrice compositionaccording to claim 1 wherein the dentifrice composition is aconcentrated dentifrice that will be diluted prior to use or during use.7. The dentifrice composition according to claim 1 wherein thedentifrice composition comprises more than one gel network.
 8. Adentifrice composition according to claim 1, further comprising awhitening agent.
 9. A dentifrice composition comprising: a) a gelnetwork phase comprising: i) from about 1% to about 6%, by weight of thedentifrice composition, of one or more fatty amphiphiles comprisingcetyl alcohol and stearyl alcohol; ii) from about 0.1% to about 10%, byweight of the dentifrice composition, of a secondary surfactantcomprising sodium lauryl sulfate iii) at least about 50%, by weight ofthe dentifrice composition, of a solvent selected from the groupconsisting of sorbitol, glycerin, water, and combinations thereof; b) anoral carrier phase comprising: a fluoride compound and an abrasivepolishing material; wherein the gel network phase is used to structurethe dentifrice composition; wherein the rheology of the dentifricecomposition enables the dentifrice composition to be easily dispensedfrom a container and stand-up on a toothbrush head after the compositionis dispensed; and wherein the dentifrice composition foams when used ina conventional manner for cleansing teeth.
 10. A dentifrice compositionof claim 9 wherein the dentifrice composition comprises a viscosity fromabout 15 to about 50 BKU.
 11. A dentrifrice composition of claim 9wherein the dentifrice composition comprises a deaerated specificgravity from about 1.1 to about 1.6.
 12. A dentifrice composition ofclaim 9 wherein the dentifrice composition further comprises a moistfeeling in the mouth when used in the conventional manner for cleansingteeth.
 13. A dentifrice composition of claim 9 wherein the rheology ofthe dentifrice composition enables the composition to comprise low or nostringiness when dispensed.
 14. A dentifrice composition of claim 9wherein the dentifrice composition can be easily dispersed in a mouthand can be rinsed from the mouth when used in the conventional mannerfor cleansing teeth.
 15. A dentifrice composition comprising: a) a gelnetwork phase comprising: i) from about 1% to about 6%, by weight of thedentifrice composition, of one or more fatty amphiphiles comprisingcetyl alcohol and stearyl alcohol; ii) from about 0.1% to about 10%, byweight of the dentifrice composition, of a secondary surfactantcomprising sodium lauryl sulfate; iii) a solvent selected from the groupconsisting of sorbitol, glycerin, water, and combinations thereof; b) anoral carrier phase comprising: a fluoride compound and an abrasivepolishing material; wherein the gel network phase is used to structurethe dentifrice composition.
 16. A process for preparing a foamingdentifrice composition comprising the steps of: a) combining from about0.05% to about 30%, by weight of the dentifrice composition, of a fattyamphiphile wherein said fatty amphiphile is a combination of cetylalcohol and stearyl alcohol having a chain melt temperature, from about0.01% to about 15%, by weight of the composition, of a secondarysurfactant having an HLB of 6 or more, and from about 0.1% to about 99%,by weight of the composition of solvent at a temperature sufficient toallow partitioning of said secondary surfactant and said solvent intosaid fatty amphiphile to form a mixture; b) cooling said mixture belowthe chain melt temperature of said fatty amphiphile to form a gelnetwork; and c) adding oral carrier materials comprising an anionicsurfactant, a flavoring component, and an abrasive polishing material tothe gel network to form the foaming dentifrice composition.
 17. Theprocess according to claim 16 wherein some oral carriers are added instep a).
 18. The process according to claim 16 wherein some oralcarriers are added in step b).
 19. The process according to claim 16wherein the anionic surfactant added in step c) is the same as thesecondary surfactant added in step a).
 20. A method of treating the oralcavity comprising applying to the oral cavity a safe and effectiveamount of the dentifrice composition according to claim 1.